JPH0410056B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved color reproducibility. [Prior Art] A method for forming a dye image using a silver halide color photographic light-sensitive material includes a method in which a dye is formed by a reaction between a photographic coupler and an oxidized form of a color developing agent. Magenta, yellow and cyan couplers are used as photographic couplers for reproduction, and aromatic primary amine color developing agents are used as color developing agents. A dye such as an azomethine dye is formed by the reaction between the coupler and an oxidized form of an aromatic primary amine color developing agent, and a reaction between the cyan coupler and an oxidized form of an aromatic primary amine color developing agent forms a dye such as an azomethine dye.
Pigments such as indoaniline dyes are formed. Among these, in order to form a magenta image, 5-pyrazolone, cyanoacetophenone,
Indazolone, pyrazolobenzimidazole, pyrazolotriazole couplers, etc. are used. Most of the conventional magenta color image forming couplers that have been put to practical use have been 5-pyrazolone couplers. Color images formed from 5-pyrazolone couplers have excellent fastness to light and heat, but the color tone of this dye is not sufficient;
Unwanted absorption with a yellow component exists near 430 nm, and the absorption spectrum of visible light near 550 nm is also broad, causing color turbidity and making photographic images lack vividness. U.S. patent for coupler without unnecessary absorption
3725067, JP 59-162548, JP 59-171956
1H-pyrazolo[3,2-
c]-s-triazole type coupler, 1H-imidazo[1,2-b]pyrazole type coupler, 1H-
pyrazolo[1,5-b]pyrazole coupler,
Alternatively, 1H-pyrazolo[1,5-d]tetrazole type couplers are particularly excellent. However, the light fastness of dye images formed from these couplers is significantly lower. For photosensitive materials, especially photosensitive materials suitable for direct viewing,
The use of these couplers impairs the essential requirement of photographic materials to record and preserve images. Therefore, it was difficult to put it into practical use. Therefore, as a method for improving light resistance, the use of phenol-based or phenyl ether-based antioxidants is described in JP-A-59-125732, but the effect was not sufficient. [Object of the Invention] In view of the above situation, the first object of the present invention is to provide a silver halide color photographic light-sensitive material with excellent light fastness of magenta color images. A second object of the present invention is to improve the light fastness of a magenta color image formed from at least one of the above-mentioned couplers, and to provide a halogen-based image without deteriorating photographic performance such as sensitivity, gradation, whiteness, etc. Our objective is to provide silver oxide photographic materials. A third object of the present invention is to provide a silver halide photographic material in which the color reproducibility of magenta images is improved and the light fastness of magenta images is good. [Structure of the Invention] The object of the present invention is to combine at least one coupler represented by the following general formula [] with at least one of the compounds represented by the following general formula [XI] and [XII]. This is achieved by a silver halide photographic material containing one of the following. General formula [] In the formula, R ₁ and R ₂ each represent a different substituent, and X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. General formula [XI] General formula [XII] In the formula, X ¹ , X ² and X ⁴ each represent an oxygen atom. X ³ represents a hydroxyl group, Y represents an oxygen atom or a sulfur atom, and R ¹ , R ² and R ³ each represent a hydrogen atom or an alkyl group. However, R ¹ ,
At least two of R ² and R ³ represent an alkyl group. R ⁴ to ^{R 9} are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acylamino group, an alkylamino group, a carbamoyl group, a sulfamoyl group, a sulfonamido group, and a sulfonyl group. group or cycloalkyl group. Further, they may be connected to each other to form a 5- or 6-membered ring. M represents a metal atom. a, b,
c, d, e and f each represent an integer of 0 to 4. Next, the present invention will be specifically explained. The above general formula according to the present invention [] General formula [] In the magenta coupler represented by R ₁
Examples of the substituent represented by _R2 include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, and a cyano group. , spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group. Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R ₁ and R ₂ preferably has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group preferably have 2 to 32 carbon atoms, and the alkyl group, alkenyl group, and alkynyl group are linear But it can also be a branch. In addition, these alkyl groups, alkenyl groups, and alkynyl groups include substituents (for example, aryl, cyano, halogen atoms, heterocycles, as well as those substituted via a carbonyl group such as acyl, carboxyl, carbamoyl, alkoxycarbonyl, and heterocycles). Those that are substituted through an atom, specifically those that are substituted through an oxygen atom such as hydroxyl, alkoxy, and aryloxy; those that are substituted through a nitrogen atom such as nitro and amino (including dialkylamino, etc.); (such as those substituted via a sulfur atom such as alkylthio). Specifically, for example, methyl group, ethyl group, t-butyl group, pentadecyl group, heptadecyl group, 1,
1-dipentylnonyl group, 2-chloro-t-butyl group, trifluoromethyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4
-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonamide phenoxypropyl group, 3-
4′-{α-[4″-(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4′-[α-(2″,4″-di-t
-amylphenoxy)butanamide]phenyl}
Propyl group, 4-[α-(o-chlorophenoxy)
Examples include tetradecanamidophenoxy]propyl group, allyl group, and the like. The aryl group represented by R ₁ and R ₂ is preferably a phenyl group, which may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4
-tetradecanamide phenyl group, hexadecyloxyphenyl group, 4'-[α-(4''-t-butylphenoxy)tetradecanamide] phenyl group, etc. Heterocyclic group represented by R ₁ and R ₂ As for 5~
7-membered ones are preferred, and may be substituted,
Further, they may be condensed. Specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-
Examples include benzothiazolyl group. Examples of the acyl group represented by R ₁ and R ₂ include alkylcarbonyl groups such as acetyl group, phenylacetyl group, dodecanoyl group, α-2,4-di-t-amylphenoxybutanoyl group, and benzoyl group. group, 3-pentadecyloxybenzoyl group, p
Examples include arylcarbonyl groups such as -chlorobenzoyl group. As the sulfonyl group represented by R ₁ and R ₂ ,
Examples include alkylsulfonyl groups such as methylsulfonyl group and dodecylsulfonyl group, and arylsulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group. As the sulfinyl group represented by R ₁ and R ₂ ,
Alkylsulfinyl groups such as ethylsulfinyl group, octylsulfinyl group, 3-phenoxybutylsulfinyl group, arylsulfinyl group such as phenylsulfinyl group, m-pentadecylphenylphinyl group Examples include groups. The phosphonyl group represented by R ₁ and ₂ includes an alkylphosphonyl group such as a butylphosphonyl group,
Examples thereof include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups. The carbamoyl group represented by R ₁ and R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N
-(2-pentadecyloxyethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl group, and the like. The sulfamoyl group represented by R ₁ and R ₂ is an alkyl group, an aryl group (preferably a phenyl group)
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, etc. may be substituted. Examples thereof include a moyl group and an N-phenylsulfamoyl group. The bridged hydrocarbon compound residues represented by R ₁ and R ₂ include, for example, bicyclo[2.2.1]heptane-
1-yl, tricyclo[3.3.1.1 ³⁷ ]decane-1-
yl, 7,7-dimethyl-bicyclo[2.2.1]heptan-1-yl, and the like. The alkoxy group represented by R ₁ and R ₂ may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group, a pentadecyloxy group. , 2-dodecyloxyethoxy group, phenethyloxyethoxy group, and the like. The aryloxy group represented by R ₁ and R ₂ is preferably phenyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, p-t -butylphenoxy group, m-pentadecylphenoxy group, etc. The heterocyclic oxy group represented by R ₁ and R ₂ preferably has a 5- to 7-membered heterocycle,
The heterocycle may further have a substituent, for example, 3,4,5,6-tetrahydropyranyl-2
-oxy group, 1-phenyltetrazole-5-oxy group, and the like. The siloxy group represented by R ₁ and R ₂ may be further substituted with an alkyl group, and examples thereof include a siloxy group, a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. As the acyloxy group represented by R ₁ and R ₂ ,
Examples include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc., which may further have substituents, specifically acetyloxy groups,
Examples include α-chloroacetyloxy group and benzoyloxy group. The carbamoyloxy group represented by R ₁ and R ₂ is
It may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group,
Examples include N,N-diethylcarbamoyloxy group and N-phenylcarbamoyloxy group. The amino group represented by R ₁ and R ₂ is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, m-chloroanilino group, 3-pentadecyloxycarbonylanilino group, 2-chloro-5-
Examples include hexadecaneamide anilino group. As the acylamino group represented by R ₁ and R ₂ ,
Examples include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, an α-ethylpropanamide group, an N- phenylacetamide group,
Dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl-4
-hydroxyphenoxybutanamide group and the like. Examples of the sulfonamide group represented by R ₁ and R ₂ include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specific examples include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group. The imide group represented by R ₁ and R ₂ may be open-chain or cyclic, and may have a substituent, such as succinimide group, 3-heptadecylsuccinimide group, phthalimide group, etc. group, glutarimide group, etc. The ureido group represented by R ₁ and R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-methyl-N-decylureido group, and an N-ethylureido group.
-phenylureido group, N-p-tolylureido group, etc. The sulfamoylamino group represented by R ₁ and R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N, N
-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group and the like. The alkoxycarbonylamino group represented by R ₁ and R ₂ may further have a substituent,
Examples include methoxycarbonylamino group, methoxyethoxycarbonylamino group, octadecyloxycarbonylamino group, and the like. The aryloxycarbonylamino group represented by R ₁ and R ₂ may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group. The alkoxycarbonyl group represented by R ₁ and R ₂ may further have a substituent, such as a methoxycarbonyl group, a butoxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyl group, a benzyloxy Examples include carbonyl group. The aryloxycarbonyl group represented by R ₁ and R ₂ may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group etc. The alkylthio group represented by R ₁ and R ₂ may further have a substituent, such as an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group. The arylthio group represented by R ₁ and R ₂ is preferably a phenylthio group, and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3
-octadecyl phenylthio group, 2-carboxyphenylthio group, p-acetaminophenylthio group and the like. As the heterocyclic thio group represented by R ₁ and R ₂ ,
A 5- to 7-membered heterocyclic thio group may further have a condensed ring or a substituent. For example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,
A 3,5-triazole-6-thio group is mentioned. Examples of the atom that can be released by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.). In addition, examples of groups that can leave include carbon atoms,
Examples include groups substituted via an oxygen atom, sulfur atom or nitrogen atom, and a carboxyl group. As a group substituted via a carbon atom, for example, the general formula (R ₁ and R ₂ have the same meaning as R ₁ and R ₂ in the general formula [], and R ₃ and R ₄ are hydrogen atoms, aryl groups,
Represents an alkyl group or a heterocyclic group. ), a hydroxymethyl group, and a triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyl groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. can be mentioned. The alkoxy group may further have a substituent,
For example, ethoxy group, 2-phenoxyethoxy group,
2-cyanoethoxy group, phenethyloxy group, p
-chlorobenzyloxy group and the like. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4-methanesulfonamide phenoxy group, 4-[α-(3'-pentadecylphenoxy)butanamide] phenoxy group, hexadecylcarbamoylmethoxy group, 4-
Examples thereof include a cyanophenoxy group, a 4-methanesulfonylphenoxy group, a 1-naphthyloxy group, and a p-methoxyphenoxy group. The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, and may be a fused ring,
Moreover, it may have a substituent. Specifically, 1
-phenyltetrazolyloxy group, 2-benzothiazolyloxy group and the like. Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoyloxy groups, alkenylcarbonyloxy groups such as cinnamoyloxy groups, and arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkoxycarbonylthio group. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. The arylthio group includes a phenylthio group,
4-methanesulfonamidophenylthio group, 4-
Examples include dodecylphenethylthio group, 4-nonafluoropentanamidophenethylthio group, 4-carboxyphenylthio group, and 2-ethoxy-5-t-butylphenylthio group. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the group substituted via the nitrogen atom include the general formula

Examples include those represented by the formula. Here R ₅ and R ₆ are hydrogen atoms, alkyl groups,
It represents an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, or an alkoxycarbonyl group, and R ₅ and R ₆ may be combined to form a heterocycle. However, R ₅ and R ₆ are not both hydrogen and snow atoms. The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group, and a sulfone group. Amide group, imino group, acyl group,
Alkylsulfonyl group, arylsulfonyl group,
Examples include carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group, and halogen atom. Specific examples of the alkyl group include ethyl group, octyl group, 2-ethylhexyl group,
A 2-chloroethyl group is mentioned. The aryl group represented by R ₅ or R ₆ preferably has 6 to 32 carbon atoms, particularly a _phenyl group or a naphthyl group, and the aryl group may have a substituent. Alternatively, the substituents for the alkyl group represented by R ₆ include those listed above and an alkyl group. Specific examples of the aryl group include phenyl group, 1-naphthyl group, and 4-methylsulfonylphenyl group. The heterocyclic group represented by R ₅ or R ₆ is 5 to
A 6-membered ring is preferred, and may be a fused ring,
It may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidinyl group,
Examples include 2-benzothiaryl group and 2-pyridyl group. Examples of the sulfamoyl group represented by R ₅ or R ₆ include N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc. These alkyl groups and aryl groups may have the substituents listed above for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group,
Examples include N-dodecylsulfamoyl group and N-p-tolylsulfamoyl group. As the carbamoyl group represented by R ₅ or R ₆ ,
Examples include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups can be substituted with the substituents listed above for the alkyl groups and aryl groups. It may have a group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, and Np-tolylcarbamoyl group. Examples of the acyl group represented by R ₅ or R ₆ include an alkyl carbonyl group, an aryl carbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You can leave it there. Specific examples of the acyl group include hexafluorobutanoyl group,
2,3,4,5,6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-furylcarbonyl group. As the sulfonyl group represented by R ₅ or R ₆ ,
Alkylsulfonyl group, arylsulfonyl group,
A heterocyclic sulfonyl group may be mentioned, which may have a substituent, and specific examples include an ethanesulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p
-chlorobenzenesulfonyl group and the like. The aryloxycarbonyl group represented by R ₅ or R ₆ may have any of the substituents listed above for the aryl group, and specific examples thereof include a phenoxycarbonyl group. The alkoxycarbonyl group represented by R ₅ or R ₆ may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. Can be mentioned. The heterocycle formed by combining R ₅ and R ₆ is preferably a 5- to 6-membered one, and may be saturated or unsaturated, and may or may not have aromaticity, Alternatively, it may be a condensed ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4
-dioxoxazolidinyl group, 2-N-1,1
-dioxo-3-(2H)-oxo-1,2-benzothiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1
-imidazolyl group, 1-imidazolinyl group, 1-
Indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-
Benzotriazolyl group, 1-benzimidazolyl group, 1-(1,2,4-triazolyl) group, 1-
(1,2,3-triazolyl) group, 1-(1,2,
3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3,4-tetrahydroquinolyl group,
Examples include 2-oxo-1-pyrrolidinyl group, 2-1H-pyridone group, phthaladione group, 2-oxo-1-piperidinyl group, and these heterocyclic groups include alkyl group, aryl group, alkoxy group, aryloxy group, Acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group,
May be substituted with a sulfonamide group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, cyano group, carboxyl group, halogen atom, etc. . Also, the substituents R ₁ and R ₂ in the general formula [] are (wherein R ₁ , R ₂ and X have the same meanings as R ₁ , R ₂ and . Regarding the substituents in the general formula [], it is preferable that at least one of R ₁ and R ₂ is a tertiary alkyl group. More preferably R ₁ is 3
This is the case for a class alkyl group. Here, tertiary alkyl refers to an alkyl in which no hydrogen is bonded to the root carbon. Next, specific examples of typical magenta couplers according to the present invention will be shown, but the present invention is not limited thereto. The synthesis of the coupler is also published in the Journal of the
Chemical Society, Perkin I (1977), 2047~
The synthesis was carried out with reference to US Pat. No. 2052, US Pat. The couplers of the invention are usually 1 x 10 ^-3 mol to 5 x 10 ^-1 mol per mol of silver halide, preferably 1 x
It can be used in a range of 10 ^-2 mol to 5 x 10 ^-1 mol. The couplers of the present invention can also be used in combination with other types of magenta couplers. Furthermore, when the silver halide photographic material according to the present invention is used as a multicolor photographic material, in addition to the coupler of the present invention, yellow couplers and cyan couplers commonly used in this industry are used in the usual manner. be able to. Furthermore, if necessary, a colored coupler having a color correction effect or a coupler (DIR coupler) that releases a development inhibitor during development may be used. Two or more of the above couplers can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. As the cyan coupler and yellow coupler used in the present invention, a phenol-based or naphthol-based cyan coupler and an acylacetamide-based or benzoylmethane-based yellow coupler are used, respectively. These yellow couplers include, for example, U.S. Patent Nos. 2778658, 2875057, 2908573,
3227155, 3227550, 3253924, 3227155, 3227550, 3253924,
No. 3265506, No. 3277155, No. 3341331, No. 3265506, No. 3277155, No. 3341331, No.
No. 3369895, No. 3384657, No. 3408194, No. 3369895, No. 3384657, No. 3408194, No.
No. 3415652, No. 3447928, No. 3551155, No.
No. 3582322, No. 3725072, No. 3894875, German Patent Publication No. 1547868, No. 2057941, No. 2162899,
2163812, 2218461, 2219917, 2218461, 2219917,
No. 2261361, No. 2263875, Special Publication No. 1977-13576,
JP-A-48-29432, JP-A No. 48-66834, JP-A No. 49-
No. 10736, No. 49-122335, No. 50-28834 and No.
It is described in No. 50-132926, etc. As a cyan coupler, for example, the US patent
No. 2369929, No. 2423730, No. 2434272, No.
No. 2474293, No. 2698794, No. 2706684, No.
No. 2772162, No. 2801171, No. 2895826, No. 2895826, No. 2801171, No. 2895826, No.
No. 2908573, No. 3034892, No. 3046129, No. 3046129, No.
No. 3227550, No. 3253294, No. 3311476, No. 3227550, No. 3253294, No. 3311476, No.
No. 3386301, No. 3419390, No. 3458315, No. 3458315, No. 3419390, No. 3458315, No.
No. 3476563, No. 3516831, No. 3560212, No. 3560212, No. 3516831, No. 3560212, No.
No. 3582322, No. 3583971, No. 3591383, No. 3582322, No. 3583971, No. 3591383, No.
No. 3619196, No. 3632347, No. 3652286, No. 3619196, No. 3632347, No. 3652286, No.
No. 3737326, No. 3758308, No. 3779763, No.
No. 3839044, No. 3880661, German patent publication
No. 2163811, No. 2207468, Special Publication No. 39-27563,
45-28836, JP-A No. 47-37425, 50-
No. 10135, No. 50-25228, No. 50-112038, No. 50
−117422, No. 50-130441, No. 53-109630,
No. 50-65134, No. 56-99341 and Research Disclosure 14853
(1976) and others. In the present invention, the metal complex represented by the general formula [XI] and the general formula [XII] (hereinafter collectively referred to as the metal complex according to the present invention) may be one type, or the metal complex represented by each general formula It is also possible to use two or more kinds of compounds represented by the above formula or one or more kinds of compounds represented by each general formula. In either case, the object of the present invention can be fully achieved. X ¹ , X ² and X ⁴ in general formulas [XI] and [XII] are
Each represents an oxygen atom, and ^X3 represents a hydroxyl group. Y in general formulas [XI] and [XII] is (general formula [XII]
(Y may be the same or different) represents an oxygen atom or a sulfur atom, preferably a sulfur atom. In general formulas [XI] and [XII], R ⁴ to ^{R 9} are
Each alkyl group (for example, a straight or branched alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, t-octyl group, n-hexadecyl group, etc.) group), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy group (e.g. methoxy group, n-
butoxy group, t-butoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkoxycarbonyl group (e.g., n-pentyloxycarbonyl group, t-pentyloxycarbonyl group, n-octyl group) oxycarbonyl group, straight chain or branched alkyloxycarbonyl group such as t-octyloxycarbonyl group),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, etc.), acyl group (e.g. acetyl group,
Straight chain or branched alkylcarbonyl groups such as stearoyl group), acylamino groups (for example straight chain or branched alkylcarbonylamino groups such as acetamido group, arylcarbonylamino groups such as benzoylamino group, etc.), arylamino groups (for example N -phenylamino group, etc.), alkylamino group (e.g., linear or branched alkylamino group such as N-n-butylamino group, N,N-diethylamino group, etc.), carbamoyl group (e.g., linear chain such as n-butylcarbamoyl group) or branched alkylcarbamoyl group), sulfamoyl group (e.g. N, N
- straight-chain or branched alkylsulfamoyl groups such as di-n-butylsulfamoyl group and N-n-dodecylsulfamoyl group), sulfonamide groups (straight-chain or branched alkylsulfamoyl groups such as methylsulfonylamino group) arylsulfonylamino groups such as alkylsulfonylamino groups and phenylsulfonylamino groups), sulfonyl groups (e.g. linear or branched alkylsulfonyl groups such as mesyl groups, arylsulfonyl groups such as tosyl groups), or cycloalkyl groups (e.g. cyclohexyl group, etc.).Also, 2
The substituents may be closed to form a 5- or 6-membered ring (eg, a benzene ring). Further, M in the general formulas [XI] and [XII] represents a metal atom, preferably a nickel atom, a copper atom, a cobalt atom, a palladium atom or a platinum atom, and more preferably a nickel atom. At least two of R ¹ , R ² and R ³ in general formula [XI] are linear or branched alkyl groups (e.g. methyl group, ethyl group, n-propyl group, n-butyl group,
n-octyl group, n-hexadecyl group, etc.). These alkyl groups have substituents (for example, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups,
acylamino group, arylamino group, alkylamino group, carbamoyl group, sulfamoyl group, sulfonamide group, sulfonyl group, cycloalkyl group, etc.) may be present. Next, specific examples of typical metal complexes according to the present invention will be shown, but the present invention is not limited thereto. These complexes can be synthesized by the methods described in British Patent No. 858890, German Patent Application No. 2042652, and the like. The complex according to the present invention is preferably used in a proportion of usually 5 to 100% by weight, more preferably 10 to 50% by weight, based on the coupler according to the present invention. Further, the complex according to the present invention is preferably used in the same layer as the coupler according to the present invention, and more preferably, the complex is present in the same oil droplet. Various methods can be used to disperse the metal complexes or couplers as described above, such as the so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be appropriately selected depending on the chemical structure of the metal complex, etc. In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have been well known for a long time, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open Nos. 49-74538 and 51.
-59943, 54-32552, Research Disclosure magazine,
August 1976, No. 14850, pages 77-79. Suitable latexes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)
Ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1
- homopolymers, copolymers and copolymers of monomers such as sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxypentyl)]acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, etc. It is a terpolymer. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied.
Dissolving the above-mentioned diffusion-resistant coupler in a high boiling point solvent,
There is a method of finely dispersing it in hydrophilic colloids like gelatin. As the high boiling point organic solvent, esters such as phthalic acid esters and phosphoric acid esters, organic acid amides, ketones, hydrocarbon compounds, etc. are used, but preferably the dielectric constant is 7.5 or less and 1.9 or more at 100°C.
It is a high boiling point organic solvent with a vapor pressure of 0.5 mmHg or less. Examples of the high-boiling organic solvent used include sibutyl phthalate, dioctyl phthalate, dinonyl phthalate, trioctyl phosphate, trinonyl phosphate, tricresyl phosphate, triphenyl phosphate, and the like. The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but in particular, when color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effects of this will be effectively demonstrated. The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic colors and a non-light-sensitive layer are usually used. Although it has a structure in which layers are laminated on a support in an appropriate number and order of layers, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use. When the metal complex according to the present invention is used in combination with the magenta coupler according to the present invention, a favorable light fastness effect can be obtained in terms of specific reactivity. Therefore,
The metal complex according to the present invention is contained in a silver halide emulsion layer containing the magenta coupler according to the present invention, usually a green-sensitive silver halide emulsion layer, of a silver halide photographic light-sensitive material. A dye formed by a reaction between a magenta coupler obtained by exposing a light-sensitive material and developing it in the presence of a color developing agent and an oxidized product of the color developing agent is present in the layer holding the dye. preferable. Silver halide emulsions used in each silver halide emulsion layer constituting the silver halide photographic light-sensitive material used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, and silver iodobromide. Any of those used in conventional silver halide emulsions, such as silver chloroiodide, etc., are included. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. In addition, the crystals of these silver halide grains may be normal crystals or twin crystals, and have (100) and (111) crystals.
Any ratio to the surface can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. These silver halide grains can be prepared by known methods commonly used in the art. The particles may also be doped with iridium, rhodium, or the like. Furthermore, the photographic emulsion containing the silver halide grains may be subjected to sulfur sensitization, selenium reduction or noble metal sensitization. Optical sensitization may also be performed spectrally using various sensitizing dyes. The silver halide photographic material according to the present invention includes:
In addition to the various additives mentioned above, development accelerators, hardeners,
Surfactants, antifouling agents, lubricants, and various other useful additives may be added. As the support used in the silver halide photographic material used in the present invention, conventionally known supports such as plastic laminate, baryta paper, synthetic paper, polyethylene terephthalate film, and triacetate cellulose film can be used. The support is usually subjected to various treatments in order to strengthen the adhesion with the silver halide emulsion layer. Various coating methods such as dip coating, air doctor coating, curtain coating, and slide hopper coating can be used to coat the silver halide emulsion layer and non-photosensitive layer used in the present invention. The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 g per color developer, preferably about 1 g to about 30 g per color developer.
Use at a concentration of approximately 15g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. A particularly useful primary aromatic amine color developer is an N,N-dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N,N-diethyl-
p-phenylenediamine hydrochloride, N-methyl-p
-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-
5-(N-ethyl-N-dodecylamino)toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline , 4-amino-3-methyl-N,N-
Examples include diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, and the like. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, and the like may optionally be included. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as the bleaching agent in the bleaching process, and the metal complex oxidizes the metallic silver produced during development to convert it into silver halide, and at the same time colors the uncolored part of the color former. Its composition is aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid, which are
Coordinated with metal ions such as cobalt and copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] ] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) ) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminetetraacetic acid pentasodium salt [17] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt [18] Propylene Diaminetetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, as well as various additives. can be included. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, metal salts, chelating agents, and the like. In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, and borax. , sodium hydroxide, potassium hydroxide,
It may contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. ,
For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. [Example] The present invention will be explained in more detail with reference to specific examples below, but the embodiments of the present invention are not limited thereto. Example 1 40 g of the exemplified magenta coupler (A-2) was dissolved in a mixed solvent of 40 ml of dioctyl phthalate and 100 ml of ethyl acetate, and this solution was added to 300 ml of a 5% gelatin aqueous solution containing sodium dodecylbenzenesulfonate, followed by a homogenizer. Disperse the resulting dispersion into a green-sensitive silver chlorobromide emulsion (500g).
(containing 30 g of Ag) and a coating aid was added thereto to prepare a coating solution. Next, this coating solution was coated on a polyethylene-coated paper support, and 2-(2'-hydroxy-3',5'-di-t) was further coated on this coated layer.
A coating solution containing -amylphenyl)benzotriazole, gelatin, a spreading agent, and a hardening agent was applied to form a protective film. At this time, 2-(2'-hydroxy-3',5'-di-t
-Amyl phenyl) benzotriazole is 5 mg/
dm ² and gelatin was applied in an amount of 15 mg/dm ² to prepare a silver halide photographic light-sensitive material, which was designated as Sample 1. Next, Samples 2 to 7, which were the same as Sample 1 except that the metal complexes according to the present invention were added to the emulsion layer of Sample 1 in the combinations shown in Table 1, were prepared. A sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.,
After performing optical wedge exposure using a KS-7 model, the following processing was performed. Standard processing steps (processing temperature and processing time) [1] Color development 38℃ 3 minutes 30 seconds [2] Bleach-fixing 33℃ 1 minute 30 seconds [3] Washing 25-30℃ 3 minutes [4] Drying 75~ 80℃ for about 2 minutes Processing solution composition (color developing tank liquid) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N-(β-methanesulfonamidoethyl)aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water Set the total amount to 1 and adjust the pH to 10.20. (Bleach-fix tank solution) Ferric ammonium ethylenediaminetetraacetate 2
Water salt 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 1. After the treatment, the light resistance of the obtained sample was measured as follows. [Lightfastness test] The color fading rate (D ₀ − D / D ₀ ×100, D ₀ initial density ( 1.0), D (density after fading) were measured. These results are shown in Table 1.

[Measurement of spectral reflection density spectrum of magenta colored sample]

The spectral reflection spectrum of the magenta colored portion of each sample was measured using Color Analyzer Model 607 (manufactured by Hitachi, Ltd.). At this time, the maximum concentration of the absorption spectrum in the visible region of each sample was normalized to 1.0 and measured. The reflection density at 420 nm of each sample was taken as the sub-absorption density and used as a measure of color purity. These results are shown in Table 2.

[Table] Yes.
Comparison magenta coupler Comparative metal complex-1 and comparative antioxidant-1 are the same as in Example-1. As is clear from Table 2, the combination of the metal complex according to the present invention and the magenta coupler according to the present invention is more effective than the combination with Comparative Antioxidant-1 and Comparative Metal Complex-1. It can be seen that the effect of improving light resistance is greater than that of the combination with magenta coupler. In particular, this effect is expressed by the general formula []
This is remarkable when the group represented by R ₁ in the magenta coupler according to the present invention is a tertiary alkyl group. These facts were completely unexpected. Further, in the sample of the present invention, a magenta image with good color purity and good light fastness was obtained. Example 3 An antihalation layer consisting of a subbed cellulose triacetate film (black colloidal silver
0.40g and 3.0g gelatin. ) Sample 24 was prepared by coating each of the following layers in order on a transparent support. 1st layer: Low-sensitivity layer of red-sensitive silver halide emulsion layer 1.8 g of silver iodobromide emulsion (emulsion) color sensitized to red sensitivity and 0.8 g of 1-hydroxy-4-(β
-methoxyethylaminocarbonylmethoxy)-
N-[δ-(2,4-di-t-amylphenoxy)
butyl]-2-naphthamide (referred to as C-1),
0.075 g of 1-hydroxy-4-[4-(1-hydroxy-8-acetamido-3,6-disulfo-
2-naphthylazo)phenoxy]-N-(δ-(2,
4-di-t-amylphenoxy)butyl]-2-
naphthamide disodium (referred to as CC-1),
0.015 g of 1-hydroxy-2-[δ-(2,4-
0.65 g of 4-octadecylsuccinimide-2-(1-phenyl-5-tetrazolylthio)-1-indanone (referred to as D-1), 0.07 g of di-t-amylphenoxy)-n-butyl]naphthamide;
A low-speed layer of a red-sensitive silver halide emulsion layer containing a dispersion dissolved in tricresyl phosphate (referred to as TCP) and emulsified and dispersed in an aqueous solution containing 1.85 g of gelatin. 2nd layer: High-sensitivity layer of red-sensitive silver halide emulsion layer: 1.2 g of silver iodobromide emulsion (emulsion) color sensitized to red sensitivity and 0.21 g of cyan coupler (C-1)
and 0.02g colored cyan coupler (CC-1)
A high-sensitivity layer of a red-sensitive silver halide emulsion layer containing a dispersion that is dissolved in 0.23 g of TCP and emulsified and dispersed in an aqueous solution containing 1.2 g of gelatin. 3rd layer: middle layer 0.8g gelatin and 0.07g 2,5-di-t
- an intermediate layer containing 0.04 g of dibutyl phthalate (referred to as DBP) in which octylhydroquinone (referred to as HQ-1) is dissolved; 4th layer: Low-sensitivity layer of green-sensitive silver halide emulsion layer 0.80g of the emulsion color-sensitized to green sensitivity,
A low-sensitivity layer of a green-sensitive silver halide emulsion layer containing a dispersion in which 0.80 g of Exemplified Compound (A-5) and 0.01 g of diethyl lauryl amide were emulsified and dispersed in an aqueous solution containing 2.2 g of gelatin. . 5th layer: High-sensitivity layer of green-sensitive silver halide emulsion layer 1.8g of emulsion color-sensitized to green sensitivity,
0.25g dissolved in 0.20g of exemplary compound (A-5)
A high-sensitivity layer of a green-sensitive silver halide emulsion layer containing a dispersion obtained by emulsifying and dispersing diethyl lauryl amide in an aqueous solution containing 1.9 g of gelatin. 6th layer: Yellow filter 0.15g of yellow colloidal silver, 0.11g of DBP in which 0.2g of color stain inhibitor (HQ-1) is dissolved, and 1.5g of yellow colloidal silver.
Yellow filter layer containing g of gelatin. 7th layer: Low sensitivity layer of blue-sensitive silver halide emulsion layer 0.2g of emulsion color sensitized to blue sensitivity and 1.5g of blue-sensitive silver halide emulsion layer.
g of α-pivaloyl-α-(1-benzyl-2-
Phenyl-3,5-dioxoimidazolidine-4
-yl)-2-chloro-5-[α-dodecyloxycarbonyl)ethoxycarbonyl]acetanilide (referred to as Y-1) was dissolved in 0.6 g of TCP.
Low-sensitivity layer 8th layer of blue-sensitive silver halide emulsion layer containing a dispersion emulsified in an aqueous solution containing 1.9 g of gelatin: High-sensitivity layer of blue-sensitive silver halide emulsion layer Iodobromide Contains a dispersion in which 0.9 g of a silver emulsion sensitized to blue sensitivity and 0.65 g of TCP in which 1.30 g of yellow coupler (Y-1) is dissolved are emulsified and dispersed in an aqueous solution containing 1.5 g of gelatin. Highly sensitive blue-sensitive silver halide emulsion layer. 9th layer: Protective layer 0.23g gelatin protective layer. Samples 25 to 29 were prepared with the exception of sample 24 prepared in this manner, except that 40 mol % of the metal complex shown in Table 3 was added to the coupler in the green-sensitive emulsion layer. Moreover, trioctyl phosphate (sample 30) and dioctyl phthalate (sample 31) were used in place of diethyl lauryl amide as the high-boiling organic solvent in the fourth and fifth layers of sample 29. After each of the samples 24 to 31 thus prepared was wedge exposed using green light, the following development treatment was performed. Development process Color developer 38℃ 3 minutes 15 seconds Bleaching solution 38℃ 4 minutes 20 seconds Washing with water 38℃ 3 minutes 15 seconds Fixing solution 38℃ 4 minutes 20 seconds Washing with water 38℃ 3 minutes 15 seconds Stable solution 38 Dry at 47°C ± 5°C for 16 minutes 30 seconds The composition of the color developing solution used is as follows. Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g Sodium diethylenetriaminepentaacetate 2.5g 4-Amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1, potassium hydroxide or 20
Adjust the pH to 10.06 using % sulfuric acid. The composition of the bleaching solution used is as follows. Ethylenediaminetetraacetic acid iron ammonium salt
100g Ethylenediaminetetraacetic acid 10g Ammonium bromide 150g Glacial acetic acid 40ml Sodium bromate 10g Add water to make 1, and adjust the pH to 3.5 using aqueous ammonia or glacial acetic acid. The composition of the fixer used is as follows. Ammonium thiosulfate 180g Anhydrous sodium sulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetic acid 0.5g Sodium carbonate 10g Add water to make 1. The composition of the stabilizing solution used is as follows. Formalin (37% aqueous solution) 2ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 5ml Add water to make 1. The light resistance of the sample obtained as described above was examined in the same manner as in Example 1. The results are shown in Table 3.

〔Effect of the invention〕

To significantly improve the light resistance of the magenta coupler according to the present invention, which has good color purity and is useful as a two-equivalent coupler, by combining it with the metal complex according to the present invention, which acts specifically reactively on the magenta coupler. was completed.

Claims (1)

[Scope of Claims] 1 Contains at least one coupler represented by the following general formula [] and at least one of the compounds represented by the following general formula [XI] and [XII] A silver halide photographic material characterized by: General formula [] [In the formula, R ₁ and R ₂ each represent a different substituent, and X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. ] General formula [XI] General formula [XII] [In the formula, X ¹ , X ² and X ⁴ each represent an oxygen atom. X ³ represents a hydroxyl group, Y represents an oxygen atom or a sulfur atom, and R ¹ , R ² and R ³ each represent a hydrogen atom or an alkyl group. However, R ¹ ,
At least two of R ² and R ³ represent an alkyl group. R ⁴ to ^{R 9} are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acylamino group, an alkylamino group, a carbamoyl group, a sulfamoyl group, a sulfonamido group, and a sulfonyl group. group or cycloalkyl group. Further, they may be connected to each other to form a 5- or 6-membered ring. M represents a metal atom. a, b,
c, d, e and f each represent an integer of 0 to 4. ]